Journal of Molecular Structure, 30 (1976) 243-253

oEisevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

MOLECULAR STRUCTURE OF BENZENE

KOICHI TAMAGAWA, TAKAO IIJIMA and MASAO KIMURA

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo (Japan)

(Received 24 January 1975)

ABSTRACT

The molecular structure of benzene has been determined by combining the average
distances obtained by the present electron diffraction study and the moments of inertia
reported by Cabana et al. The following thermal average bond distances have been deter-
mined: rg(C-C) = 1.399 + 0.001 A and r,(C-H) = 1.101 -c 0.005 A. The uncertainties
represent the estimated limits of error. The C-H distance of this molecule is similar to
vinyl C-H distances.

INTRODUCTION

It is often found that the structural data of the most basic molecules are
not very up-to-date because such molecules were studied in the early stages
of the development of experimental methods for structure determination.
Benzene is one such molecule.
The molecular structure of benzene in the gas phase was determined by
means of electron diffraction [l-3] and Raman spectroscopy [4, 51; the
values determined by the previous electron diffraction studies, ra(C-C) =
1.397 i- 0.004 A and r,(C-H) = 1.08 f 0.02 a, have often been quoted as
the interatomic distances of this molecule. Since these values were obtained
more than a decade ago, we thought it worthwhile to reinvestigate the
structure of benzene using modem experimental and analytical facilities. In
the midst of our present study, an electron diffraction reinvestigation of
benzene has also been performed by Seip et al. [6,7] and Beagley and
Hewitt [S] , independently. In view of the importance of benzene,
however, we have completed the structure determination using the latest
spectroscopy results in addition to those we obtained by electron diffraction.
The combined use of diffraction and spectroscopic data has been success-
ful in the determination of accurate structures of gas molecules [9-111. In
the present study, bond lengths were determined independently by electron
diffraction and utilisation of spectroscopic results, then combined use of
them was made in order to obtain the most reliable values of the structural
parameters.
In the initial stage of the present study, we used the rotational constants
244

observed by Stoicheff by means of Raman spectroscopy [4]. Recently,

Cabana et al. obtained the rotational constants of benzene by high resolu-
tion IR spectroscopy [12] . Since their values seem to be more accurate than
those by Stoicheff, these were used in the present report to determine the
structural parameters.

ELECTRON DIFFRACTION

Experimental

A sample of benzene specially prepared for spectroscopic use was obtained

from the Nakarai Chemicals Co., Ltd. and used without further purification.
Diffraction photographs were taken with an apparatus described previously
1131.The experimental conditions were as follows: accelerating voltage,
40-42 kV; camera lengths, 10.93 and 24.43 cm; sample pressure, 40-60
torr; exposure time, 80-100 s; electron-beam current, -0.1 PA; room
temperature, 292-295 K. In order to calibrate the accelerating voltage, the
diffraction patterns of carbon disulfide were taken just before those of the
sample in the same sequence of exposure *. The data were reduced following
our routine procedure 1171. Ten plates, five plates each from the long and
short camera lengths, were selected for analysis. The data adopted for
analysis covered the ranges of s values, 3-20 and 7-41 Xl, for the long and
short camera lengths, respectively.
The experimental leveled total intensity curves and the experimental
background curves for arbitrarily selected plates are shown in Fig. l**. At
larger scattering angles, s > 26, the background curve for the short camera
length turned up gradually. Since the photographs taken without injection
of gases were perfectly transparent, this extraneous scattering may be
mainly due to the reflection of scattered electrons at the inner wall of the
sector race. This tailing-up effect was eliminated by subtracting this
extraneous background, which was assumed to be given by the deviation of
the experimental background, from the theoretical value [17]. The radial
distribution curve corresponding to the curve from the short camera length
shown in Fig. 1 is depicted in Fig. 2.

*Walker et al. have recently redetermined the rotational constant, B,, of carbon disulfide
by means of laser Raman spectroscopy [ 143. By using their constant, the r=(C-S)
distance was calculated to be 1.5569 a. We have so far used the value, r,(C-S) = 1.5570 A
[15], which was determined from the B, value observed by Stoicheff [16]. Fortunately,
the difference between the two r,(C-S) values is so small that it has no effect upon the
results of our previous structure determinations.
**The experimental total intensity data and error matrices have been deposited with the
British Library Lending Division at Boston Spa, Yorkshire, U.K. as Supplementary
Publication No. 26015 (9 pages).
 245

Long comera range

Short camero range 1.1

10

Fig. 1. Total intensities and experimental backgrounds leveled by the theoretical

background.

10 20 30 40
r-C%)

Fig. 2. Observed radial distribution curve for benzene and the residuals. Vertical lines
mark interatomic distances.

Strut tural analysis

The molecular parameters were determined by applying the least-squares

method to the molecular intensity. The moIecuIe was assumed to have &I.,
symmetry in equilibrium. The geometry is, then, defined by the C-C and
C-H bond distances. Following the method of Hedberg and Iwasaki [lS] , all
of the eight non-bonded distances were restricted under the geometrical
constraint of the ra structure. All the parallel and perpendicular mean
amplitudes were fixed at the values calculated by Brooks and Cyvin [ 19,20].
The asymmetry parameters, K, for the bonded pairs were estimated by
means of the diatomic approximation 1211 to be 1.5 X 10m6and 11.8 X
10m6A3 for the C-C and C-H bonds, respectively, and those for all non-
bonded pairs were assumed to be zero. The Hartree-Fock-based elastic 1221
and inelastic atomic scattering factors 1231 were used.
The structural parameters, r,, obtained by the least-squares refinements
and the thermal average distances, rg, derived from r, are shown in Table 1
with their limits of error, which were estimated to be 2.6 times the standard
errors with additional account of the systematic error [17] *. The indices of
resolution were 0.972-0.993 and 0.914-0.947 for the long and short camera
lengths, respectively. The errors in the scale factor were estimated to be
0.07 %, a value corresponding to an error of 0.001 A for the C-C distance.
The differences in the C-H distance between the results from the two camera
Iengths is about 0.011 A. However, no significant discrepancy is observed
between the results for the C-C distance. There was no substantial change in
the C-C distance and its standard deviation when the least-squares iterations
were carried out by fixing the r,(C-H) parameter at a value in the range of
1.097-1.108 A. This is due to the very weak scattering power of the hydro-
gen atoms. The final ra values were determined by taking the weighted
average of the results from the two camera lengths, and their limits of error
were taken so as to cover the limits of error of both results. The theoretical
intensity curves calculated by the best-fit parameters and the residuals are
shown in Fig. 3. The C-C distance thus determined agrees well with those
reported in the previous papers, while the C-H distance is longer than the
previous values [l-5] by 0.02 A.

TABLE 1

Results of the least-squares analysis of benzene (in i\ units)

rc-c ‘C-H

Cameralength(cm) 24.43 10.93 Average” 24.43 10.93 Averagea

5 1.3976 1.3967 1.3971 1.1079 1.0974 1.1018

=t b 0.0002 0.0002 0.0013 0.0018
=t b 0.0001 0.0002 0.0003 0.0006
‘g 1.3991 1.3982 1.3986 1.1133 1.1028 1.1072
Limit_ of error 0.0013 0.0013 0.0018= 0.0061 0.0052 0.0113=

=The average of the results from the two camera lengths.

bThe definitions of U, and (Jo are given in ref. 24.
%rcludes systematic errors from various sources, see text.

*The sources of systematic errors taken into consideration were as follows: uncertainty
involved in the determination of the scale factor, uncertainty in the parameter, K,
uncertainty in the correction curve for the sector shape, delocalization of the sample gas,
arbitrariness of the background curves and arbitrariness of the weight function.
 247

Fig_ 3. Molecular intensities for benzene. Theoretical curves calculated by the use of the
best-fit parameters and the residuals, sM(.s)ObS - SMUT

COMBINED USE OF DIFFRACTION AND SPECTROSCOPIC DATA

Zero-point moment of inertia

The high resolution IR spectrum of benzene has been studied by Cabana

et al. 1121. They obtained the rotationaI constants of C6H6 and C6D6. The
effective moments of inertia were converted into the zero-point moments of
inertia by correcting for the vibrational effect. The correction procedure is
well established [25-28). The force constants of the internal potential field
determined by Cabfano and Crawford for the in-plane vibrations 1291 and
those determined by Brooks and Cyvin for the out-of-plane vibrations 1191
were used in the calculation, the same force constants being assumed for the
two isotopic species*. The uncertainties inI,,CZ)were estimated from the errors
included in the experimental moments of inertia, I, MO,and those involved in the
conversion from Ibceff)to IbcZ),the latter of which were roughly assumed to
be 26 5%of the correction values. The correction for the electronic interaction
[26] was ignored.

*Our calculated frequencies agreed well with those reported by Caiifano and Crawford
except for the E,,v,, mode of vibration of benzene-d,, for which we obtained a frequency
higher by 30 cm-‘. The reason for this discrepancy is not known. However, this mode of
vibration makes only an insignificant contribution to the mean amplitude_ Therefore, no
further refinement of the force constants was made.
248

TABLE 2

Moments of inertia of benzene (in amu .X2units)

AI,b

C6H, 88.781 (~CJ)~ - 0.041 (8) 88.822 (13)

C,D.% 107.339 (18) 0.032 (7) 107.371 (20)

aDerived from the B, values observed by Cabana et al. 1121 by using the conversion
factor, 16.8575 amu A2 cm-‘.
bCorrection for the vibrational effect.
%ero-point moments of inertia, It,(‘) = fdeff) + AI,.
dValues in the parentheses are uncertainties in 10m3amu AZ units.

Isotope effect on the zero-point structure

In order to determine the P-~structure* from the moments of inertia for

several isotopic species, the primary and secondary isotope effects on the rZ
distances should be estimated. The vibrational averages of the linear dis-
placements along the equilibrium bond direction at absolute zero tempera-
ture, <AZ>,, were obtained by the use of the calculated parallel and perpen-
dicular mean amplitudes and the Morse anharmonicity parameters [ll] .The
numerical values of <Az>~ calculated for the bonded distances of the two
isotopic species are tabulated in Table 3. The Morse anharmonicity parameters
for the C-C and C-H bonds were assumed to be 2.1 and 2.0 K’, respectively
1321. As may be seen from Table 3, the r,(C-D) may be expected to be
shorter by 0.0002 a than the r,(C-H).

TABLE 3

Isotope effect on rz distances. Calculated values of <AZ>, (in lo* X units)

C-C C-H( C-D)

GH, 43 15
GD, 42 13

Conversion of rg into ri

The rz distance can be derived from the rg distance by using the anhar-
manic stretching, <Ar>, the perpendicular mean amplitudes at zero
temperature, KO, and the centrifugal distortion, 6 rcent[ 101. The centrifugal
terms were estimated by balancing the centrifugal force with Hooke’s
restoring forces of the C-C and C-H bonds. The numerical values for this

*The definitions of various average distances, rz, rg and rav, are given in refs. 30 and 31.
 249

TABLE 4

Numerical values of the correction terms in reducing rg to I-g(in lo-“ A units)

<Pr> KS ’ rcent
r -r"
K Q

CC 1 24 2 27(3)=
C-H 0 164 0 164(6)

=Values in parentheses are limits of error.

TABLE 5

Zero-point average structure of benzene (in A units)

b
‘g
C-C 1.395, 0.001, 1.396, 0.000, 1.396, 1.399, 0.000,
C-H 1.091 0.012 1.083 0.006 1.085 1.101 0.005

=Limits of error for the r”, or rz distances.

bEstimated from the r distances_
CLimits of error for thzvt-=”and rg distances.

conversion are listed in Table 4. The ?-i structures of benzene thus derived
are listed in the first column of Table 5 along with their limits of error
which were estimated from the errors of the rEdistances and those involved
in the conversion.

Zero-point auerage s true ture

When D,, symmetry is assumed for the present molecule, the b-moment
of inertia can be expressed in terms of the two parameters, r, (C-C) and
r,(C-H), by the equation,
Ibcz)= 3{m,(rZCC)z + mH(rzcC + rzcEz)2} (1)
The rz structure of this molecule can, therefore, be determined from the
spectroscopic data alone by using the estimated values of the isotopic
differences in the rz distances. From the observed I,,(=) values of C6Hs and
C,D, in Table 2 and the isotopic differences in Table 3, the r, values were
determined as shown in Table 5.
Figure 4 shows the C-C and C-H distances obtained and their limits of
error. In Fig. 4 a spectroscopically allowed range for each species is confined
by the parallel lines which represent the limits of error. The width of the
parallel line allowed from Ib(Z)(CsD6) was determined fkom the errors of the
1b~z)(C6D,) and those involved in the isotopic differences. The parallelogram
enclosed by the solid lines, therefore, indicates the region of the parameter
allowed by the spectroscopic data. The uncertainties involved in the a values
250

l.lOC

1.09-
Q-=x
z

L
c 1oe-

1 1
1.394 1396 1390
t-K-C)(~)

Fig. 4. Relation between r(C-C) and r(C-H). A parallelogram shows a region of values
allowed by the two moments of inertia and an ellipse shows the limits of error of the
diffraction data-The points ED and SP represent the values obtained by electron diffrac-
tion and spectroscopy, respectively. The straight line shows the direction of possible
variation of rz(C-C) and rg(C-H) when a systematic error is allowed for in the scale
factor of the diffraction data.

I
1.396 1397
Tz (C-C 1 (E 1

Fig. 5. The rz values obtained using various sets of a values. (1) e&c = 2-l and cC__H =
2.0 K’; (2) cc_ = 2.1 and q-H = 2.5; (3) acs = 2.1 and“C__H = 1.5; (4) acS = 2.6
andac_H = 2.0; (5) ocx = 1.6 and eC__H = 2.0.

were assumed to be + 0.5 tS_’ for both the C-C and C-H bonds. The in-
fluence of the a values upon the rz structure is illustrated in Fig. 5. The
small circles show the r,yalues obtained by using several sets of a values
which were taken within their assumed uncertainties. As may be seen, the a
value for the C-H bond has much greater influence upon the results than
does that for the C-C bond. The errors due to the uncertainty in the 0: value
 251

unount to about one-half as much as the quoted limits of error for the
results.
The most reliable values of the distances were determined by the combined
use of the r: distances and the moments of inertia. The two parameters
r,(C-C) and r,,(C-H) were adjusted so as to minimize the weighted sum
of the squares of residuals,
R = F W, {rE(obs) - r,” I:, + z, IV,. {1,<=’(obs) - Ib e) (talc) ) ;:n (2)
where the summations were taken over the two distances and the two
moments of inertia. The relative weighting factors for the observed values
were given as being inversely proportional to the squares of the limits of
error. The weighting factor for Ib w (&De), however, was estimated by adding
the uncertainty in the isotopic difference to the limit of error. The results are
shown in Table 5. The limits of error of these parameters were estimated from
the limits of error of the observed values by applying the law of propagation
of errors. The moments of inertia calculated using the structural parameters
thus obtained agree well with the observed values as shown in Table 6.

DISCUSSION

The C-C distance, r,(C-C) = 1.399 A, determined in the present study

agrees with the value, r, = 1.399 A, determined by Seip et al. [S, 71 and
Beagley and Hewitt [8]. The C-H distance, r,(C-H) = 1.101 A, is similar
to the vinyl C-H distances, r,(C-H) = 1.10-1.11 A [33].
Diehl and Niederberger have recently observed the direct couplings from
the analysis of the H-spectrum of partially oriented l-‘3C-benzene by the
NMR spectra, and they determined the ratio rzH/rgC to be 0.788 * 0.001 by
applying the vibrational corrections to the effective distances obtained from
the direct couplings [ 343. Their ratio is slightly greater than the result of
the present study, 0.777 2 0.004. This might indicate that the interatomic
distances of benzene change possibly on going from the gas phase to the
liquid crystal solvent*.
As stated in the introduction, the structure was also determined by using
the data obtained by Stoicheff [4] . The results were as follows: ‘; (C-C) =
1.3976 + 0.0015, r,(C-H) = 1.085 + 0.010, rav(C-C) = 1.3971 2 0.0012 and
r,,(C-H) = 1.088 2 0.009 a. In comparison with those listed in Table 5, the
agreement in the C-C distance between the ED and SP results has been
improved by using the data. by Cabana et al.

*Diehl and Niederberger have concluded from the agreement between their NhIR spectro-
scopic result and our preliminary electron diffraction result that there is no detectable
change in the interatomic distances on changing from the gas phase to the liquid crystal
solvent. However, it has been found finally that the C-H distance in our early stage of
the present study was somewhat too long.
252

TABLE 6

Comparison of moments of inertia (in amu ti units)

ED (c~Ic)~ SP (obs)u ED + SP (calc)c

$,o,(’ (C,H,) 88.85 -t 0.32 88.822 I 0.013 88.821

$,(=) (CD,) 107.50 + 0.48 107.371 f 0.020 107.388

aCa.Iculated from the r: distances given in Table 5.

bSee Table 2.
CCaIculated from the ra,, distances determined by the combined use of the ED and SP
data.

ACKNOWLEDGEMENTS

We would like to thank Professor Cabana, Sherbrooke University, for

allowing us to use his experimental results before publication. We also wish
to thank Professor Kozo Kuchitsu, the University of Tokyo, for his critical
reading of the manuscript. Numerical computations were carried out on a
FACOM 230-60 of the Hokkaido University Computing Center and also on a
FACOM 270-20 of Professor Kimio Ohno’s laboratory. The authors’ thanks
are due to him.

NOTE ADDED IN PROOF

A more precise B0 value of carbon disulfide was determined by high reso-

lution IR spectroscopy. (G. Blanquet, J. W&and and C. P. Courtoy, Ann.
Sot. Sci. Bruxelles, 87 (1973) 387.) It is perfectly consistent with that of
Ref. 14.

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